TW525314B - Fuel cell and method for preparation thereof - Google Patents

Abstract

The present invention provides a fuel cell which is easy to manufacture and excellent in performance. The fuel cell of the present invention comprises a fuel electrode and an oxygen electrode arranged oppositely to each other via an electrolytic membrane. The fuel electrode and the oxygen electrode include a needle-like carbonaceous material and are directly formed on the electrolytic membrane. A needle-like carbonaceous material includes carbon nano-tube and needle-like graphite. A method of directly forming a fuel electrode and an oxygen electrode on an electrolytic membrane can be, for example, a spray method and a dripping method. A needle-like carbonaceous material such as carbon nano-tube forms an intertwined membrane structure to allow electrodes to be directly formed on an electrolytic membrane.

Description

525314 A7 B7 V. Description of the invention () — ^ [Technical field to which the invention belongs] The present invention relates to a fuel cell, and more particularly to a manufacturing method of t. "[Known technology] Dianian yelled loudly for the necessity of alternative green energy that can replace petrochemical fuels such as petroleum, such as hydrogen fuel. Hydrogen contains a large amount of chemical energy per unit mass. It is a green and inexhaustible ideal energy source for reasons such as the use of parent materials or global warming gases. In addition, especially recently, the development of fuel cells that can extract electricity from hydrogen energy has been vigorously implemented, and it is expected that it will be used as a power source for electric vehicles and other applications from large-scale power generation to local power generation. [Problems to be Solved by the Invention] A fuel cell is configured by holding a fuel cell (such as a hydrogen electrode) and an oxygen electrode while holding an electrolyte membrane, and then supplying fuel (hydrogen) or oxygen to these electrodes to generate a battery reaction and obtain electricity. In the manufacture, an electrolyte membrane, a fuel electrode, and an oxygen electrode are generally formed separately, and then bonded together. However, when the above-mentioned fuel electrode or oxygen electrode is formed separately, its handling is difficult ', which causes various inconveniences. For example, when considering the strength of a fuel electrode or an oxygen electrode, there must be a certain thickness (for example, 100 or more). However, if the thickness of the electrode is increased, the efficiency of the battery reaction will be reduced, and the battery performance will be reduced. To avoid this, if the thickness of the electrode is reduced, it cannot be processed into a self-supporting film, and the manufacturing yield is greatly reduced.

525314 V. Description of the invention (The present invention was proposed in view of such knowledge, and the purpose is to provide a fuel tank that is easy to manufacture and has excellent battery performance for its manufacturing method. The inventor has accumulated various researches to achieve the above-mentioned objective. The result is that needle-shaped carbonaceous materials such as carbon nanotubes are entangled with each other: a membrane structure w, which can be used to directly form an electrode on an electrolyte membrane. It is proposed based on the results of such experiments. That is, the present invention = fuel cell is equipped with a fuel electrode and an oxygen electrode, and these fuel cells are arranged opposite to each other via an electrolyte membrane, and are characterized by : The above fuel electrode and / or oxygen electrode are made of needle-shaped carbonaceous material, and are directly formed on the above-mentioned electrolyte membrane. Also, the manufacturing method of the present invention includes a fuel electrode and an oxygen electrode. The electrolyte membranes are arranged to face each other, and are characterized in that the fuel electrode and / or the milk electrode containing a needle-like carbonaceous material are applied by a drip coating method or dripped. And the like are directly formed on the above-mentioned electrolyte membrane. Z In the present invention, 'the electrode containing needle-like carbonaceous material is directly formed on the #electrolyte membrane, [the fuel electrode or the electrode does not need to be treated separately, and The mechanical strength is considered. Therefore, the thickness of these electrodes can be reduced. As a result, the produced fuel cell-based battery reacts efficiently and the battery performance can be improved. [Embodiments of the Invention] The following relates to a fuel cell to which the present invention is applied. Please refer to the drawing for detailed description of the method of making the paper. 5- 297 mm) I paper according to the standard (CNS) 525314 A7

The structure of the fuel cell is basically as shown in the previous figure. It has ion conductivity (the two surfaces of the electrolyte membrane are formed with a fuel electrode 2 and an oxygen electrode 3 ° respectively. Then, the fuel electrode 2 is supplied with ammonia, for example. If oxygen is supplied to the oxygen electrode 3: a battery reaction occurs and electric power is generated. Here, when the fuel electrode 2 is a so-called direct methanol method, methanol can also be supplied. If the electrolyte membrane i has ion conductivity, it can be used as Any. For example, a material having ion conductivity can be applied to the separation membrane. Specifically, a material that can be used for this electrolyte M1 can be, for example, a perfluorinated acid resin [for example, manufactured by DuPont, trade name] Nafi〇n (R), etc.] proton (hydrogen ion) conductive polymer materials. Also, relatively new proton conductors can also use a H3M〇i2p〇4〇 · 29H2〇 or Sb205 · 5.4h2 〇 Many waters and polycopper acids or oxides of water 0 When these polymer materials or water and compounds are placed in a wet state, they exhibit high proton conductivity near normal temperature. That is, if a perfluorosulfonic acid resin is used as example, The ionized protons of the sulfonic acid group are in the polymer matrix combined with a large amount of absorbed water (hydrogen bonding) and protonated water, which is to generate oxygen ions (H3O +). In the y state, the protons can move smoothly in the polymer matrix, so the name of this matrix material can also play a fairly high proton conduction effect at room temperature. Or, it can also be completely different from this material conduction mechanism. Conductor 0 is a composite η with perovskite structure such as doped YbiSrCe〇3

line

525314 A7 B7 V. Description of the invention (4) Metal oxides. The composite metal oxide having such a # 5 'mineral structure can exhibit proton conductivity even when water is used as a mobile medium. In this composite metal oxide, protons are conducted in a separate channel between oxygen ions that form the skeleton of the perovskite structure. Further, a proton conductor that constitutes the above-mentioned electrolyte membrane 1 and a carbonaceous material containing carbon as a main component as a matrix, and a proton conductor having a proton dissociative base introduced therein may be used. Here, the "proton dissociative base" means a functional group capable of separating protons (H +) by ionization. Specifically, examples of the proton dissociative group include -OH, -0S03H, -S03H, -COOH, -OP (OH) 2, and the like. In this proton conductor, the protons move through the proton-dissociative base, and ionic conductivity appears. As the carbonaceous material used as the precursor, any material can be used as long as it contains carbon as its main component. However, after the proton dissociative base is introduced, the ion conductivity must be greater than the electron conductivity. Specific examples include carbon atom aggregates, that is, carbonaceous materials containing carbon clusters or tubular carbonaceous materials (so-called carbon nanotubes). There are many types of carbon errors mentioned above, and it is advisable to use fullerene or at least a part of the fullerene structure with open ends and those with wrong stone structures. Hereinafter, this carbon cluster will be described in more detail. The above group 1 is generally an aggregate formed by combining or aggregating several to several hundred atoms. When this atom is carbon, the agglomeration (aggregation) improves the proton conductivity while maintaining the chemical properties and the membrane strength is sufficient. Easy to form layers. In addition, the so-called "cluster with carbon as the main component" refers to the species regardless of the combination of carbon and carbon.

Binding

525314 A7 ____B7 V. Description of the invention (~ 7 ~), and an aggregate formed by combining several to hundreds of carbon atoms. However, it is not necessarily limited to those composed of 100% carbon, and other atoms may be mixed. It also includes the case where the aggregate of carbon atoms is called carbon hafnium. If this assembly is illustrated graphically (however, the proton dissociation base system is not shown), as shown in Figures 2 to 5, the choice of raw materials for the proton conductor is wide. Here, as shown in FIG. 2, the carbon atoms are composed of a plurality of aggregates, and various carbon clusters having a sphere, a long sphere, or a closed structure similar to these (however, molecular fullerenes are also shown in combination). Similar to this, various types of carbon atoms that are partially missing in these sphere structures are shown in FIG. 3. At this time, it is characterized by having an open end in the structure, so that the structural system is a common by-product in the fuUerene manufacturing process of arc discharge. If most of the carbon atoms are sp3 bonded, they become a cluster with various diamond structures as shown in Figure 4. Fig. 5 shows the situation where various groups are mistakenly combined. Such a structure can also be applied to the present invention. A proton conductor containing a carbonaceous material having a base capable of bonding with the above-mentioned protons as a main component, the protons are easily dissociated from the aforementioned bases even in a dry state. Moreover, this proton exhibits high conductivity across a wide temperature range (at least about 160 C 4 0 C) including normal temperature. In addition, as described above, the mussel conduction m shows sufficient proton conductivity even in a dry state, but there is no problem with the presence of water (this water can also be immersed from the outside). In the present invention, either or both of the fuel electrode 2 and the oxygen electrode 3 are directly formed on the electrolyte membrane 1 composed of the above-mentioned materials. At this time, the household electrode is directly formed, and the electrode must have a needle-shaped carbonaceous material such as carbon nanotubes or needle-shaped stones (for example, manufactured by Toho Corporation, trade name Vgcf, etc.). The paper size is 1 €. Sample Standard (CNS) Regulation 8 (21〇χ 297 · =) ----- 525314 A7 B7 V. Description of the Invention (Materials). Figure 6 is an arc light used to make a carbonaceous material containing carbon nanotubes. An example of a discharge device. In this device, a cathode 12 and an anode 1 3 each of which is made of a graphite carbon rod in a reaction chamber 11 of a so-called vacuum chamber are arranged opposite to each other through a gap G. The anode 1 The rear end of 3 is connected to the linear motion introduction mechanism 1 4, and each pole is connected to the current introduction terminals 15 a and 15 b. In this configuration, the reaction chamber 11 is degassed and filled with an inert gas such as helium. Direct current is applied to each electrode, and a light distribution discharge is generated between the cathode 12 and the anode 13, and a medium-like substance is deposited on the inner surface of the reaction chamber 11, that is, the side wall surface, the top surface, the bottom surface, and the cathode 12. Carbonaceous material. If a small container is installed in advance on the side wall surface, etc., the carbonaceous material also accumulates in it. Recovered from the reaction chamber 11 The powdery carbonaceous material contains carbon nanotubes as shown in FIG. 7 (A), C60fullerene shown in FIG. 7 (B), C70 fullerene (not shown), and FIG. 7 (c). Medium carbon, etc. This medium carbon is a medium that has the curvature of fullerene molecules or carbon nanotubes. If the typical composition of a carbonaceous material like this is cited, C60, C70, etc. are replaced by ... 10-20%, carbon nanotubes are several%, and a large amount of intermediate carbon is contained in the carbonaceous material. In addition, in the above carbonaceous material, at least the surface thereof has a mechanism for separating water molecules into hydrogen ions to further separate them. Proton and electron catalyst energy metals should support 10% by weight or less by known methods. Examples of metals with catalyst energy include platinum or platinum alloys. If such metals are supported, they should not be supported. Time-phase friends can improve the efficiency of battery reaction. Use needle-like carbon-free materials to directly form the fuel electrode 2 or oxygen electrode 3 on the electrolyte membrane. However, the formation method here can be lifted or dropped.

525314

law. In the case of the graft method, the carbonaceous material is dispersed in a solvent containing water, ethanol, or the like, and then blown directly onto the electrolyte membrane 1. In the case of the dropping method, the above-mentioned carbonaceous material is dispersed in a solvent containing water, ethanol, or the like, and then dropped directly on the electrolyte membrane i. Thereby, the above-mentioned carbonaceous material is deposited on the electrolyte membrane 1. At this time, the above-mentioned carbon nanotube system has a diameter of about 1 nm and a length of… and a long, fibrous shape, and the acicular graphite also has a diameter of about 0 to 0.5 mm and a length of about 1 to 5 0 / / m is a needle-like shape, so they are entangled with each other and can form a good layered body even if a special binder is provided. Of course, if necessary, a binder can be used together. The fuel electrode 2 or oxygen formed as described above The electrode 3 does not need to be a self-supporting film, and therefore does not require mechanical strength. Therefore, the thickness of the electrode 3 can be set to be very thin, for example, about 2 to 4 vm. After manufacturing the fuel cell by the above method, it can be obtained with A fuel cell with a capacity of 100 mW. It is also an electrode in which carbon nanotubes or needle-shaped graphite is directly formed on the electrolyte membrane 1 by spraying or dropping, and it has good adhesion to the electrolyte membrane and does not cause peeling. Table 1 shows the results of measuring the peeling frequency with the ratio R [= VG-CF / (CNT + VGCF)] of the carbon nanotube (CNT) to the needle-shaped graphite (VGCF). The peeling frequency S is based on an adhesive tape. For a film of area 9, it was measured For comparison, Table 1 also shows the value of the peeling frequency S when carbon ink or graphite is used. ___- 10- This paper uses the Chinese National Standard (CNS) A4 specification (210 X 297 mm). (Centi) 525314 V. Description of the invention ([Table 1

CNT + VGCF carbon black graphite (3 # m) Use: Carbon nanotubes or needles have a large volume, and the right side of the graphite temple, it can be seen that the surface that remains without peeling is peeling adhesion. However, when carbon black or graphite is used, it is obvious that the use of "'*" is not enough, and when it is used as an electrode, the adhesion is insufficient. The structure of the fuel cell manufactured here is shown in FIG. 8. , = This fuel cell has a negative electrode (fuel electrode or hydrogen electrode) 2 8 and a positive electrode (oxygen electrode) 29 which make the catalysts 2 7 a and 2 7 b respectively close or dispersed and face each other. Proton conducting body 30 is held between the poles. From these negative electrodes 28 and positive technology 29, pull out the terminals 2ga and 29a to form a structure for connection to an external circuit. 'When this fuel cell is used, hydrogen is supplied from the inlet 3 1 on the negative electrode 28 side and discharged from the discharge port 3 2 (this is not sometimes provided). Fuel (η 2) 3 3 will generate protons through the flow path 3 4. The protons move in the proton conducting body 3 〇 11 The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 525314

When it reaches the positive electrode 29, it is supplied from the introduction port 35 to the flow path 36 and reacts with the oxygen (air) 38 toward the exhaust port 37 ', thereby extracting the desired electric power. In the above configuration, a carbon material for hydrogen storage, a hydrogen storage alloy, a hydrogen cylinder, and the like are stored in the hydrogen supply source 39. In addition, hydrogen can be stored in this material in advance, or it can be stored in a hydrogen supply source 89. [Effects of the Invention] As can be seen from the above description, according to the present invention, it is possible to provide a fuel cell which is easy to manufacture and has excellent battery performance. In addition, in the manufacturing method of the present invention, the fuel electrode or the oxygen electrode does not need to be processed individually, and no complicated work is required, which can greatly improve the manufacturing yield. [Brief Description of Drawings] FIG. 1 is a schematic sectional view showing a basic structure of a fuel cell. FIG. 2 is a schematic diagram showing various examples of carbon clusters. Fig. 3 is a schematic diagram showing another example (partially fuuerene structure) of carbon hafnium. FIG. 4 is a schematic diagram showing another example (diamond structure) of carbon clusters. Fig. 5 is a schematic diagram showing another example of a carbon cluster (an inter-group bonder). Fig. 6 is a schematic view showing an example of an arc discharge device for forming a carbon nanotube. Figures 7 (A) ~ (C) are schematic diagrams of various carbonaceous materials contained in carbon powder produced by arc discharge, (A) is a schematic diagram of a cylindrical carbon material, and (B) is a spherical_carbon The schematic diagram of the material, (C) is the schematic diagram of the incomplete spherical carbon material. FIG. 8 is a schematic diagram of a specific configuration example of a fuel cell. The paper size is suitable for s B family materials (CN;) weaving grid 挪 χ Norwegiano love) 525314 A7 B7 V. Description of the invention (1 () [Symbol description] 1 Electrolyte membrane 2 Fuel electrode 3 Oxygen electrode __- 13- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm).

Claims (1)

d 厶 丄 4 Type L fuel cells, printed and patented by the Central Standards Bureau of the Ministry of Economic Affairs, with the scope of patent application. These fuel cells are equipped with a fuel electrode, stomach + life # + 1 and a lice electrode. These fuel electrical characteristics are based on electrolyte membranes. The fuel electrode and / or the oxygen electrode are arranged to face each other, and the fuel electrode and / or the oxygen electrode are formed of needle-shaped carbonaceous material and are formed on the electrolyte membrane. 2. The fuel cell according to the patent patent ㈣β, wherein the fuel electrode and / or oxygen electrode having the needle-shaped carbonaceous material described above has a thickness of ≤ or less. 3. The fuel cell according to item i of the application, wherein the needle-shaped carbonaceous material is a carbon nanotube. "Based on the scope of patent application! The fuel cell according to item 1, wherein the needle-shaped broken material is needle-shaped graphite. 5. · A method for manufacturing a fuel cell, comprising a fuel electrode and an oxygen electrode, wherein the fuel electrode and the oxygen electrode are arranged to face each other via an electrolyte membrane, and is characterized in that a needle-like carbon The fuel electrode and / or oxygen electrode of the material is directly formed on the electrolyte membrane. 6. The method for manufacturing a fuel cell according to item 5 of the scope of patent application, wherein a fuel electrode and / or an oxygen electrode containing the needle-shaped carbonaceous material is directly formed on the electrolyte membrane by a nozzle coating method or a dropping method. -14- (Please read the note on the back page first) --- Ding% This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)